CN108470633A - A kind of electrode material for super capacitor of the excellent cyclical stability of height ratio capacity - Google Patents
A kind of electrode material for super capacitor of the excellent cyclical stability of height ratio capacity Download PDFInfo
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- CN108470633A CN108470633A CN201810335280.XA CN201810335280A CN108470633A CN 108470633 A CN108470633 A CN 108470633A CN 201810335280 A CN201810335280 A CN 201810335280A CN 108470633 A CN108470633 A CN 108470633A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, chemical formula V4C3Tx, wherein T is hydroxyl, fluorine atom or oxygen atom, 0≤x≤2.The invention discloses the preparation methods of the electrode material for super capacitor of the excellent cyclical stability of above-mentioned height ratio capacity, pass through chemical stripping its presoma MAX phase compounds V4AlC3In Al atomic layers and obtain.The quality specific capacitance of resulting materials of the present invention reaches 203F/g at 2mV/s, and under 10A/g current densities after 4000 constant current charge-discharges, specific capacitance conservation rate is up to 88.34%, lays a good foundation for its application in being commercialized electrode material.
Description
Technical field
The present invention relates to electrode material for super capacitor technical field more particularly to a kind of excellent cyclical stabilities of height ratio capacity
Electrode material for super capacitor and preparation method thereof.
Background technology
With the fast development of global economy, the mankind are continuously increased the consumption of fossil energy, and energy crisis and environment are dirty
The problems such as dye, is increasingly prominent, therefore explores energy-saving and environmental protection, efficient new energy technology and new energy materials as current Energy Section
The problem of learning with material science urgent need to resolve.Ultracapacitor has power density height, charge and discharge as a kind of new type of energy storage device
The advantages that electric speed is fast, service life is long, safe to use, pollution-free promises to be this century novel green power supply.It is super
Capacitor is mainly made of electrode material, diaphragm, electrolyte and encapsulating material, and the quality of wherein electrode material performance directly affects
The main performance of ultracapacitor, therefore it is most crucial in ultracapacitor research to develop the electrode material with excellent properties
Project.
Currently, the common electrode material of ultracapacitor have conducting polymer composite (polypyrrole, polyaniline, polythiophene with
And their derivative etc.), carbon materials (activated carbon, carbon nanotube, carbon fiber, graphene etc.), metal oxide (ruthenium-oxide
Deng), double-metal hydroxide etc..However, above-mentioned electrode material respectively has advantage and disadvantage, such as there is cycle surely in conducting polymer composite
The problems such as qualitative poor, specific capacitance is small, self discharge is serious；Metal oxide is although specific capacitance is larger, stable circulation and forthright again
It can be poor；Carbon materials are although have preferable cyclical stability and high rate performance, specific capacitance less.Therefore, develop
Electrode material for super capacitor with high-specific capacitance super, excellent cycling stability, high rate capability is that the current field is badly in need of
The major issue of solution.
In the recent period, a kind of New Two Dimensional MX alkene materials being made of early transition metal M and carbon/nitrogen X, due to electromagnetic shielding,
Heavy metal ion adsorbed, ion/molecular filtering, photothermal conversion, sensor etc., especially in the side such as electrode material for super capacitor
There is very excellent performance in face, is more and more paid close attention to and studies by people.
MX alkene is typically to corrode its forerunner by chemical reagent (hydrofluoric acid, lithium fluoride/sodium/potassium+hydrochloric acid, ammonium acid fluoride etc.)
Body MAX phases compound (chemical formula Mn+1AXn, M is usually early transition metal element, and A is major element, and X is carbon or nitrogen,
N=1,2,3) in A atomic layers and obtain.Stratiform MAX phase compounds are corroded MX layer of gained and graphene knot after A atomic layers
Structure is similar, and hence obtain one's name MX alkene.The preparation of MX alkene typically carries out in a solution of hydrofluoric acid, and chemical equation is as follows：
Mn+1AXn+HF→AFy+Mn+1Xn+H2 (1)
Mn+1Xn+H2O→Mn+1Xn(OH)x+H2 (2)
Mn+1Xn+HF→Mn+1XnFx+H2 (3)
Mn+1Xn+O2→Mn+1XnOx (4)
After above-mentioned chemical reaction, gained Mn+1XnThe functional groups such as-F ,-O ,-OH in the surface meeting adsorbent solution of layer,
The functional group's type and quantity adsorbed under different preparation conditions have difference, therefore the chemical formula of MX alkene is usually written as Mn+1XnTx(T
=F, OH, O etc.；0≤x≤2).The Yurg Gogotsi professors group of Drexel universities of the U.S. in 2011 reports first MX alkene
Ti3C2Tx, subsequent people obtain Ti again2CTx、Ti2NTx、V2CTx、Nb2CTx、Mo2CTx、Zr3C2Tx、Hf3C2Tx、Nb4C3Tx、
Ta4C3Tx、Ti4N3TxDeng more than 20 kind MX alkene, but its quantity, far fewer than presoma MAX phases compound (more than 70 kinds), novel MX alkene has
It waits for further synthesizing.
MX alkene material is due to the characteristics such as big specific surface area and interlamellar spacing, good electric conductivity and hydrophily, super
Grade capacitor electrode material field shows excellent performance and potential application prospect.Currently, people are super to MX alkenyls
The research of capacitor electrode material is concentrated mainly on Ti3C2Tx、Ti2CTx、Mo2CTx、V2CTx、Nb4C3TxIn, wherein Ti3C2TxIt is
By people's most study and the MX alkenyl electrode materials of best performance.Ti3C2TxItself there are higher conductivity, therefore people
Mainly its chemical property is promoted by increasing specific surface area and optimization microscopic appearance.M.R.Lulcatskaya et al. is reported
Multilayer Ti3C2TxIn 1mol/L KOH electrolyte under 1A/g current densities, volumetric capacitance 350F/cm3.Later,
M.Ghidiu et al. is by removing multilayer Ti3C2TxObtain few layer even single layer Ti3C2Tx, in 1mol/L H2SO4In electrolyte
When sweep speed is 2mV/s, volumetric capacitance is up to 900F/cm3(245F/g).In the recent period, M.R.Lulcatskaya et al. exists
Few layer Ti3C2TxMiddle addition μm grade polymethylmethacrylacontinuous (organic glass), forms porous Ti after calcining3C2TxIt is thin
Film, in 3mol/L H2SO4In electrolyte when sweep speed is 2mV/s, volumetric capacitance reaches 1500F/cm3(380F/g),
With RuO2Volumetric capacitance it is suitable；Even under the high sweep speed of 10V/s, volumetric capacitance is still up to 829F/cm3
(210F/g).Meanwhile above-mentioned Ti3C2TxBase electrode material all has good cyclical stability, in the case where current density is more than 1A/g
After constant current charge-discharge 10000 times, specific capacitance conservation rate is all 90% or more.However, surpassing in the MX alkene systems reported at present
The specific capacitance of grade capacitor electrode material is still less than the specific capacitance of oxide and double-layered hydroxides with special construction
(under 1A/g current densities specific capacitance be more than 1000F/g), therefore seek in MX alkene systems the novel MX of more high-specific capacitance super
Alkene electrode material is particularly important.
Invention content
Technical problems based on background technology, the present invention propose a kind of high-specific capacitance super, excellent cycling stability
Electrode material for super capacitor and preparation method thereof, quality specific capacitance reaches 203F/g at 2mV/s, and (volumetric capacitance is about
For 909F/cm3)。
A kind of electrode material for super capacitor of the excellent cyclical stability of height ratio capacity proposed by the present invention, chemical formula are
V4C3Tx, wherein V is vanadium atom, and C is carbon atom, and T is hydroxyl, fluorine atom or oxygen atom, 0≤x≤2.
V4C3TxStructure, component and microscopic appearance characterization it is as Figure 4-Figure 6.
A kind of preparation method of the electrode material for super capacitor for the excellent cyclical stability of height ratio capacity that the present invention also proposes,
Include the following steps：
S1, by vanadium powder, aluminium powder, graphite powder mixed grinding, tabletting is subsequently placed in the tube furnace of flowing argon gas and is sintered, cold
But sheet presoma MAX phase compounds V is obtained4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken, its starvation and steam are subjected to ball milling, then taken
Go out to be placed in hydrofluoric acid and stir, cleans, be dried to obtain the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity.
V obtained by wherein S14AlC3Structure, component and microscopic appearance characterization it is as shown in Figs. 1-3.
Preferably, in S1, vanadium powder, aluminium powder, graphite powder granularity be more than 200 mesh.
Preferably, in S1, v element, aluminium element, carbon molar ratio be 4：1-2：3.
Preferably, in S1, milling time 5-35min.
Preferably, in S1, tabletting pressure is not less than 1GPa.
Preferably, in S1, the tubular type furnace parameters for flowing argon gas are as follows：Ar pressure is more than 0.01MPa, and argon flow amount is not small
In 10mL/min.
Preferably, in S1, sintering concrete operations are as follows：1300-1600 DEG C is risen to the heating rate of 5-12 DEG C/min, is protected
The warm time is not less than 2h.
Preferably, in S1, the type of cooling is to be furnace-cooled to room temperature.
Preferably, in S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar.
Preferably, in S2, the concrete operations that its starvation and steam are carried out to ball milling are as follows：It is put in glove box
Enter in ball grinder, abrading-ball and dispersant is added, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and dispersant ball
It is taken out from glove box after grinding jar sealing, passes through ball milling instrument ball milling at least 5h.
Preferably, in the glove box of S2, oxygen content is less than or equal to 0.1ppm, and moisture content is less than or equal to 0.1ppm.
Preferably, in the ball grinder of S2, ball material mass ratio is 10-20：1.
Preferably, in S2, dispersant is alcohol.
Preferably, after S2 ball millings, presoma MAX phase compounds V4AlC3Granularity be less than 40 μm.
Preferably, in S2, the concentration of hydrofluoric acid is not less than 40wt%, presoma MAX phase compounds V after ball milling4AlC3With hydrogen
The mass volume ratio (g/mL) of fluoric acid is not more than 1：10.
Preferably, in S2, whipping temp is 40-80 DEG C, and speed of agitator is more than 300r/min, and mixing time is more than 10h.
Preferably, it in S2, is cleaned to system pH using deionized water and is more than 5.
Preferably, in S2, dry using vacuum drying, drying temperature is less than 80 DEG C.
The present invention chooses MAX phase compounds V4AlC3It is obtained for the first time after eroding Al atomic layers by hydrofluoric acid for presoma
Obtained novel MX alkene V4C3Tx, it is used as electrode material, quality specific capacitance reaches 203F/g at 2mV/s, in 10A/g electric currents
Under density after 4000 constant current charge-discharges, specific capacitance conservation rate is up to 88.34%.Therefore, V4C3TxIn ultracapacitor
The excellent properties shown in electrode material are laid a good foundation for its application in being commercialized electrode material.
Description of the drawings
Fig. 1 is 6 gained MAX phase compounds V of embodiment4AlC3Room temperature X-ray diffractogram.
Fig. 2 is 6 gained MAX phase compounds V of embodiment4AlC3Scanning electron microscope (SEM) photograph；Wherein a is V4AlC3The scanning on surface
Electron microscope；B is V4AlC3The scanning electron microscope (SEM) photograph of tomography.
Fig. 3 is 6 gained MAX phase compounds V of embodiment4AlC3Transmission electron microscope picture；Wherein a is V4AlC3The low resolution in surface
Transmission electron microscope picture；B is V4AlC3The high-resolution-ration transmission electric-lens figure of section；C is V4AlC3The high-resolution-ration transmission electric-lens figure on surface.
Fig. 4 is 6 gained MX alkene V of embodiment4C3TxRoom temperature X-ray diffractogram.
Fig. 5 is 6 gained MX alkene V of embodiment4C3TxScanning electron microscope (SEM) photograph.
Fig. 6 is 6 gained MX alkene V of embodiment4C3TxTransmission electron microscope picture；Wherein a is V4C3TxSurface low resolved transmittance electricity
Mirror figure；B is V4C3TxSection high-resolution-ration transmission electric-lens figure；C is V4C3TxSurface high-resolution-ration transmission electric-lens figure.
Fig. 7 is 6 gained V of embodiment4C3TxChemical property of the electrode in 1M KOH electrolyte；Wherein a is different scanning
V under rate4C3TxThe CV curves of electrode；B is V4AlC3And V4C3TxThe quality specific capacitance of electrode and the functional relation of sweep speed
Figure；C is the V under different current densities4C3TxThe constant current charge-discharge curve of electrode；D is in 10A g-1Lower V4C3TxElectrode follows
Ring performance, illustration show constant current loop-around data.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, includes the following steps：
S1, the vanadium powder for by granularity being 200 mesh, aluminium powder and graphite powder mixed grinding 35min, wherein v element, aluminium member
Plain, carbon molar ratio is 4：1：3；Tabletting, tabletting pressure are 3.5GPa；It is subsequently placed in the tube furnace of flowing argon gas with 5
DEG C/heating rate of min rises to 1600 DEG C and is sintered, soaking time 2.5h, the tubular type furnace parameters for flowing argon gas are as follows：Argon
Gas air pressure is 0.07MPa, argon flow amount 10mL/min, is furnace-cooled to room temperature and obtains sheet presoma MAX phase compounds V4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar, it is put into ball grinder in glove box
In, the oxygen content in glove box is 0.05ppm, and the moisture content in glove box is 0.1ppm, is 20 by ball material mass ratio：1
Abrading-ball is added, alcohol is added later, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and alcohol ball grinder sealing
It is taken out from glove box afterwards, by ball milling instrument ball milling 5h, presoma MAX phase compounds V after ball milling4AlC3Granularity be 5-35 μ
m；It then takes out to be placed in the hydrofluoric acid of a concentration of 42wt% and stir, whipping temp is 80 DEG C, and speed of agitator 350r/min is stirred
It is 14h to mix the time, presoma MAX phase compounds V after ball milling4AlC3Mass volume ratio (g/mL) with hydrofluoric acid is 1：12；Using
It is 5.2-6 that deionized water, which is cleaned to system pH, and vacuum drying, drying temperature is 75 DEG C, steady to the excellent cycle of height ratio capacity
Qualitative electrode material for super capacitor.
Embodiment 2
A kind of preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, includes the following steps：
S1, the vanadium powder for by granularity being 800 mesh, aluminium powder and graphite powder mixed grinding 5min, wherein v element, aluminium member
Plain, carbon molar ratio is 4：2：3；Tabletting, tabletting pressure are 1.5GPa；It is subsequently placed in the tube furnace of flowing argon gas with 12
DEG C/heating rate of min rises to 1300 DEG C and is sintered, soaking time 4.5h, the tubular type furnace parameters for flowing argon gas are as follows：Argon
Gas air pressure is 0.03MPa, argon flow amount 30mL/min, is furnace-cooled to room temperature and obtains sheet presoma MAX phase compounds V4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar, it is put into ball grinder in glove box
In, the oxygen content in glove box is 0.1ppm, and the moisture content in glove box is 0.05ppm, is 10 by ball material mass ratio：1
Abrading-ball is added, dispersant is added later, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and dispersant ball grinder
It is taken out from glove box after sealing, by ball milling instrument ball milling 8h, presoma MAX phase compounds V after ball milling4AlC3Granularity be
5-35μm；It then takes out to be placed in the hydrofluoric acid of a concentration of 48wt% and stir, whipping temp is 40 DEG C, speed of agitator 450r/
Min, mixing time 11h, presoma MAX phase compounds V after ball milling4AlC3Mass volume ratio (g/mL) with hydrofluoric acid is 1：
15；Deionized water is used to be cleaned to system pH as 5.2-6, vacuum drying, drying temperature is 65 DEG C, excellent to height ratio capacity
The electrode material for super capacitor of cyclical stability.
Embodiment 3
A kind of preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, includes the following steps：
S1, the vanadium powder for by granularity being 400 mesh, aluminium powder and graphite powder mixed grinding 30min, wherein v element, aluminium member
Plain, carbon molar ratio is 4：1.2：3；Tabletting, tabletting pressure are 3GPa；It is subsequently placed in the tube furnace of flowing argon gas with 6
DEG C/heating rate of min rises to 1500 DEG C and is sintered, soaking time 3h, the tubular type furnace parameters for flowing argon gas are as follows：Argon gas
Air pressure is 0.06MPa, argon flow amount 15mL/min, is furnace-cooled to room temperature and obtains sheet presoma MAX phase compounds V4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar, it is put into ball grinder in glove box
In, the oxygen content in glove box is 0.04ppm, and the moisture content in glove box is 0.02ppm, is 17 by ball material mass ratio：1
Abrading-ball is added, dispersant is added later, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and dispersant ball grinder
It is taken out from glove box after sealing, by ball milling instrument ball milling 6h, presoma MAX phase compounds V after ball milling4AlC3Granularity be
8-32μm；It then takes out to be placed in the hydrofluoric acid of a concentration of 46wt% and stir, whipping temp is 50 DEG C, speed of agitator 420r/
Min, mixing time 12h, presoma MAX phase compounds V after ball milling4AlC3Mass volume ratio (g/mL) with hydrofluoric acid is 1：
14；Deionized water is used to be cleaned to system pH as 5.2-6, vacuum drying, drying temperature is 68 DEG C, excellent to height ratio capacity
The electrode material for super capacitor of cyclical stability.
Embodiment 4
A kind of preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, includes the following steps：
S1, the vanadium powder for by granularity being 600 mesh, aluminium powder and graphite powder mixed grinding 10min, wherein v element, aluminium member
Plain, carbon molar ratio is 4：1.8：3；Tabletting, tabletting pressure are 2GPa；It is subsequently placed in the tube furnace of flowing argon gas with 10
DEG C/heating rate of min rises to 1400 DEG C and is sintered, soaking time 4h, the tubular type furnace parameters for flowing argon gas are as follows：Argon gas
Air pressure is 0.04MPa, argon flow amount 25mL/min, is furnace-cooled to room temperature and obtains sheet presoma MAX phase compounds V4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar, it is put into ball grinder in glove box
In, the oxygen content in glove box is 0.02ppm, and the moisture content in glove box is 0.04ppm, is 13 by ball material mass ratio：1
Abrading-ball is added, alcohol is added later, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and alcohol ball grinder sealing
It is taken out from glove box afterwards, by ball milling instrument ball milling 7h, presoma MAX phase compounds V after ball milling4AlC3Granularity be 8-32 μ
m；It then takes out to be placed in the hydrofluoric acid of a concentration of 44wt% and stir, whipping temp is 70 DEG C, and speed of agitator 380r/min is stirred
It is 13h to mix the time, presoma MAX phase compounds V after ball milling4AlC3Mass volume ratio (g/mL) with hydrofluoric acid is 1：13；Using
It is 5.2-6 that deionized water, which is cleaned to system pH, and vacuum drying, drying temperature is 72 DEG C, steady to the excellent cycle of height ratio capacity
Qualitative electrode material for super capacitor.
Embodiment 5
A kind of preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, includes the following steps：
S1, the vanadium powder for by granularity being 500 mesh, aluminium powder and graphite powder mixed grinding 20min, wherein v element, aluminium member
Plain, carbon molar ratio is 4：1.5：3；Tabletting, tabletting pressure are 2.5GPa；Be subsequently placed in flowing argon gas tube furnace in
The heating rate of 8 DEG C/min rises to 1450 DEG C and is sintered, soaking time 3.5h, and the tubular type furnace parameters for flowing argon gas are as follows：
Ar pressure is 0.05MPa, argon flow amount 20mL/min, is furnace-cooled to room temperature and obtains sheet presoma MAX phase compounds
V4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar, it is put into ball grinder in glove box
In, the oxygen content in glove box is 0.03ppm, and the moisture content in glove box is 0.03ppm, is 15 by ball material mass ratio：1
Abrading-ball is added, alcohol is added later, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and alcohol ball grinder sealing
It is taken out from glove box afterwards, by ball milling instrument ball milling 6.5h, presoma MAX phase compounds V after ball milling4AlC3Granularity be 8-
32μm；It then takes out to be placed in the hydrofluoric acid of a concentration of 45wt% and stir, whipping temp is 60 DEG C, speed of agitator 400r/
Min, mixing time 12.5h, presoma MAX phase compounds V after ball milling4AlC3Mass volume ratio (g/mL) with hydrofluoric acid is
1：13.5；Deionized water is used to be cleaned to system pH as 5.2-6, vacuum drying, drying temperature is 70 DEG C, arrives Fabrication of High Specific Capacitance
Measure the electrode material for super capacitor of excellent cyclical stability.
Embodiment 6
A kind of preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, includes the following steps：
S1, the vanadium powder for by granularity being 325 mesh, aluminium powder and graphite powder mixed grinding 15min, wherein v element, aluminium member
Plain, carbon molar ratio is 4：1.5：3；Tabletting, tabletting pressure are 1GPa；It is subsequently placed in the tube furnace of flowing argon gas with 8
DEG C/heating rate of min rises to 1500 DEG C and is sintered, soaking time 2h, the tubular type furnace parameters for flowing argon gas are as follows：Argon gas
Air pressure is 0.025MPa, argon flow amount 10mL/min, is furnace-cooled to room temperature and obtains sheet presoma MAX phase compounds V4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar, it is put into ball grinder in glove box
In, the oxygen content in glove box is 0.1ppm, and the moisture content in glove box is 0.1ppm, is 15 by ball material mass ratio：1 adds
Enter abrading-ball, alcohol is added later, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and alcohol ball grinder sealing after
It is taken out from glove box, is 30h by ball milling instrument ball milling, presoma MAX phase compounds V after ball milling4AlC3Granularity be 1-10
μm；It then taking out to be placed in the hydrofluoric acid of a concentration of 40wt% and stir, whipping temp is 55 DEG C, speed of agitator 550r/min,
Mixing time is 96h, presoma MAX phase compounds V after ball milling4AlC3Mass volume ratio (g/mL) with hydrofluoric acid is 1：10；It adopts
It is 5.5 to be cleaned to system pH with deionized water, and vacuum drying, drying temperature is 70 DEG C, steady to the excellent cycle of height ratio capacity
Qualitative electrode material for super capacitor.
The electrode material for super capacitor of the excellent cyclical stability of height ratio capacity is MX alkene V obtained by the present embodiment4C3Tx,
Middle V is vanadium atom, and C is carbon atom, and T is hydroxyl, fluorine atom or oxygen atom, 0≤x≤2.
To gained MAX phase compounds V4AlC3With MX alkene V4C3TxCarry out X-ray diffraction, scanning electron microscope, transmission electricity
Sub- microscope detection, as shown in figures 1 to 6.Again to MX alkene V4C3TxElectrochemical property test is carried out, as shown in Figure 7.
The present invention chooses MAX phase compounds V4AlC3It is obtained for the first time after eroding Al atomic layers by hydrofluoric acid for presoma
Obtained novel MX alkene V4C3Tx, it is used as electrode material, quality specific capacitance reaches 203F/g at 2mV/s, in 10A/g electric currents
Under density after 4000 constant current charge-discharges, specific capacitance conservation rate is up to 88.34%, be its in being commercialized electrode material
Application lay a good foundation.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of electrode material for super capacitor of the excellent cyclical stability of height ratio capacity, which is characterized in that its chemical formula is
V4C3Tx, wherein T is hydroxyl, fluorine atom or oxygen atom, 0≤x≤2.
2. a kind of preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity as described in claim 1,
It is characterised in that it includes following steps：
S1, by vanadium powder, aluminium powder, graphite powder mixed grinding, tabletting is subsequently placed in the tube furnace of flowing argon gas and is sintered, cooling
To sheet presoma MAX phase compounds V4AlC3；
S2, by sheet presoma MAX phase compounds V4AlC3It is broken, its starvation and steam are subjected to ball milling, then takes out and sets
It is stirred in hydrofluoric acid, cleans, be dried to obtain the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity.
3. the preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity according to claim 2,
Be characterized in that, in S1, vanadium powder, aluminium powder, graphite powder granularity be more than 200 mesh；Preferably, in S1, v element, aluminium element, carbon
The molar ratio of element is 4：1-2：3.
4. according to the preparation method of the electrode material for super capacitor of the excellent cyclical stability of height ratio capacity described in Claims 2 or 3,
It is characterized in that, in S1, milling time is 5-35 minutes；Preferably, in S1, tabletting pressure is not less than 1GPa.
5. according to the preparation of the electrode material for super capacitor of the excellent cyclical stability of any one of the claim 2-4 height ratio capacities
Method, which is characterized in that in S1, the tubular type furnace parameters for flowing argon gas are as follows：Ar pressure is more than 0.01MPa, and argon flow amount is not
Less than 10mL/min；Preferably, in S1, sintering concrete operations are as follows：1300-1600 is risen to the heating rate of 5-12 DEG C/min
DEG C, soaking time is not less than 2h；Preferably, in S1, the type of cooling is to be furnace-cooled to room temperature.
6. according to the preparation of the electrode material for super capacitor of the excellent cyclical stability of any one of the claim 2-5 height ratio capacities
Method, which is characterized in that in S2, by sheet presoma MAX phase compounds V4AlC3It is broken using mortar.
7. according to the preparation of the electrode material for super capacitor of the excellent cyclical stability of any one of the claim 2-6 height ratio capacities
Method, which is characterized in that in S2, the concrete operations that its starvation and steam are carried out to ball milling are as follows：By it in glove box
It is put into ball grinder, abrading-ball and dispersant is added, then will contain presoma MAX phase compounds V4AlC3, abrading-ball and dispersant
It is taken out from glove box after ball grinder sealing, passes through ball milling instrument ball milling at least 5h；Preferably, in the glove box of S2, oxygen content
Less than or equal to 0.1ppm, moisture content is less than or equal to 0.1ppm；Preferably, in the ball grinder of S2, ball material mass ratio is 10-20：
1；Preferably, in S2, dispersant is alcohol.
8. according to the preparation of the electrode material for super capacitor of the excellent cyclical stability of any one of the claim 2-7 height ratio capacities
Method, which is characterized in that after S2 ball millings, presoma MAX phase compounds V4AlC3Granularity be less than 40 μm.
9. according to the preparation of the electrode material for super capacitor of the excellent cyclical stability of any one of the claim 2-8 height ratio capacities
Method, which is characterized in that in S2, the concentration of hydrofluoric acid is not less than 40wt%, presoma MAX phase compounds V after ball milling4AlC3With
The mass volume ratio (g/mL) of hydrofluoric acid is not more than 1：10；Preferably, in S2, whipping temp is 40-80 DEG C, and speed of agitator is more than
300r/min, mixing time are more than 10h.
10. according to the system of the electrode material for super capacitor of the excellent cyclical stability of any one of the claim 2-9 height ratio capacities
Preparation Method, which is characterized in that in S2, cleaned to system pH using deionized water and be more than 5；Preferably, in S2, drying is adopted
With vacuum drying, drying temperature is less than 80 DEG C.
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